Methods of forming semiconductor device structures, and related structures

ABSTRACT

A method of forming a semiconductor device structure. The method comprises forming a block copolymer assembly comprising at least two different domains over an electrode. At least one metal precursor is selectively coupled to the block copolymer assembly to form a metal-complexed block copolymer assembly comprising at least one metal-complexed domain and at least one non-metal-complexed domain. The metal-complexed block copolymer assembly is annealed in to form at least one metal structure. Other methods of forming a semiconductor device structures are described. Semiconductor device structures are also described.

TECHNICAL FIELD

Embodiments of the present disclosure relate to methods of forming metalstructures for semiconductor device structures, to related methods offorming memory cells, and to related semiconductor device structures.

BACKGROUND

Integrated circuits (ICs), the key components in thousands of electronicsystems, generally include interconnected networks of electricalcomponents fabricated on a common foundation, or substrate. Metalstructures are commonly used to electrically connect semiconductorfeatures, such as capacitors or transistors, or to define a specific IC,such as a computer memory or microprocessor. The deposition andprocessing methods used to form the metal structures may affect thequality of the metal structures and impact overall manufacturability,performance, and lifetime of the IC. Thus, the methods used to form themetal structures are increasingly determining the limits in performance,density and reliability of integrated circuits.

As a non-limiting example, the deposition and processing methods used toform active electrodes for memory cells of conductive bridging randomaccess memory (CBRAM) devices may greatly affect the performance andreliability of such devices. Memory cells of CBRAM devicesconventionally utilize metallic or ionic forms of silver (Ag) or copper(Cu) to form a conductive bridge between an inert electrode and anactive electrode. The active electrode serves as the source of the Ag orCu. The conductive bridge is formed by the drift (e.g., diffusion) of Agor Cu cations (by application of a voltage across the electrodes) fromthe active electrode, through an active material of the memory cell, andto the inert electrode, where the Ag or Cu ions are electro-chemicallyreduced. The conductive bridge may be removed (by applying a voltagewith reversed polarity across the electrodes) or may remain in placeindefinitely without needing to be electrically refreshed or rewritten.

A problem with the fabrication of CBRAM devices arises due to thedifficulty of processing the Ag or Cu. For example, Cu cannot be etchedwith conventional RIE techniques, and is typically processed in adamascene flow. Also, there are currently no chemical vapor deposition(CVD) or atomic layer deposition (ALD) techniques for Ag. In addition,the ability to deposit Cu and Ag in small openings is limited.Therefore, deposition is conventionally conducted by physical vapordeposition (PVD), which limits the scalability of Ag damascene flows. Itis, therefore, currently of interest to minimize the extent of Ag or Cuprocessing during the integration and fabrication of semiconductordevices, such as CBRAM devices.

Selective deposition techniques are one way of minimizing Ag or Cuprocessing. In such techniques, pre-patterned chemical specificityenables materials, such as Ag or Cu, to be preferentially deposited onlyin desired locations, which avoid the need to etch or polish suchmaterials. Electroless plating is a conventional selective depositiontechnique. However, electroless plating exhibits variability innucleation and growth rates, which may disadvantageously result ininconsistencies in the volume of metal deposited at each site within amemory array, significantly impacting operations where the quantity ofselectively deposited metal must be critically controlled. Electrolessplating also requires substrates that are electrochemically active,whereas, in certain semiconductor devices (e.g., MOS devices, MIMdevices, and CBRAM devices), it is desirable to selectively depositmaterials to substrates that are electrochemically inactive (e.g.,dielectric materials). Accordingly, improved methods of forming metalstructures for semiconductor devices (e.g., CBRAM devices) usingselective deposition techniques are desired, as are related methods offorming memory cells.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIGS. 1A through 1E are partial cross-sectional views of a semiconductorstructure and illustrate a method of forming a metal structure for asemiconductor device structure in accordance with embodiments of thepresent disclosure;

FIGS. 2A-2F are partial cross-sectional views of a semiconductorstructure and illustrate another method of forming a metal structure fora semiconductor device structure in accordance with embodiments of thepresent disclosure;

FIGS. 3A-3E are partial cross-sectional views of a semiconductor devicestructure and illustrate yet another method of forming a metal structurefor a semiconductor device structure in accordance with embodiments ofthe present disclosure;

FIGS. 4A-4G are partial cross-sectional views of a semiconductor devicestructure and illustrate yet still another method of forming a metalstructure for a semiconductor device structure in accordance withembodiments of the present disclosure;

FIGS. 5A-5F are partial cross-sectional views of a semiconductor devicestructure and illustrate yet still an additional method of forming ametal structure for a semiconductor device structure in accordance withembodiments of the present disclosure;

FIG. 6A is a scanning electron micrograph image showing a top-down viewof copper particles formed on a semiconductor device structure, asdescribed in Example 1;

FIG. 6B is a magnified scanning electron micrograph image showing atop-down view of a single copper particle formed on a semiconductordevice structure, as described in Example 1;

FIG. 7A is a graph of Auger analysis of the single copper particle shownin FIG. 6B, as described in Example 1;

FIG. 7B is an Auger electron map of the single copper particle shown inFIG. 6B, as described in Example 1;

FIG. 8A is a scanning electron micrograph image showing a top-down viewof copper particles formed on a semiconductor device structure, asdescribed in Example 2;

FIG. 8B is a magnified scanning electron micrograph image showing atop-down view of copper particles formed on a semiconductor devicestructure, as described in Example 2;

FIG. 9A is a scanning electron micrograph image showing a top-down viewof copper particles formed on a semiconductor device structure, asdescribed in Example 2;

FIG. 9B is a magnified scanning electron micrograph image showing atop-down view of copper particles formed on a semiconductor structure,as described in Example 2;

FIG. 10A is a scanning electron micrograph image showing a top-down viewof copper particles formed on a semiconductor device structure, asdescribed in Example 2;

FIG. 10B is a magnified scanning electron micrograph image showing atop-down view of a single copper particle formed on a semiconductordevice structure, as described in Example 2;

FIG. 11A is a graph of Auger analysis of the single copper particleshown in FIG. 10B, as described in Example 2; and

FIG. 11B is an Auger electron map of the single copper particle shown inFIG. 10B, as described in Example 2.

DETAILED DESCRIPTION

Methods of forming metal structures of semiconductor device structuresare disclosed, as are related methods of forming memory cells, andrelated semiconductor device structures. The metal structure is formedfrom the selective and self-limited deposition of a metal, such ascopper (Cu), silver (Ag), or alloys thereof. The metal structure isformed by complexing a metal precursor with a polymer that is configuredto react with or couple to the metal precursor and has been applied topredetermined or patterned locations on a semiconductor substrate. Theamount of metal precursor complexed with the polymer is limited at leastby the amount of metal precursor applied to the polymer and the numberof available binding or complexing sites in the polymer. The polymer maybe removed and the metal precursor reduced to form the metal structure.By way of example and not limitation, the metal structure may be anelectrode or an interconnect. In one embodiment, the metal structure maybe used as an active electrode for a memory cell of a conductive bridgerandom access memory (CBRAM) device. As used herein, the term “activeelectrode” means and includes a conductive material, such as Cu or Ag,which serves as a source of metal ions (e.g., Cu⁺, Ag⁺) for formation ofthe conductive bridge. The metal structure may also be used as aconductive interface in a via, or as a nucleation site (e.g., a seedmaterial) for subsequent metal deposition, such as electrolessdeposition. The selective and self-limited metal deposition processesdisclosed herein may overcome difficulties with conventional processingof metals (e.g., difficulties processing Cu and Ag, such as difficultiesetching and/or depositing Cu and Ag into small structures), decrease thedeposition variability of current selective deposition technologies(e.g., electroless plating, autocatalytic deposition), and enableincreased performance in semiconductor device structures (e.g., memorycells) and semiconductor devices (e.g., CBRAM devices) that rely onspecific and uniform quantities of metal.

The following description provides specific details, such as materialtypes, material thicknesses, and processing conditions in order toprovide a thorough description of embodiments of the present disclosure.However, a person of ordinary skill in the art will understand that theembodiments of the present disclosure may be practiced without employingthese specific details. Indeed, the embodiments of the presentdisclosure may be practiced in conjunction with conventional fabricationtechniques employed in the industry. In addition, the descriptionprovided below does not form a complete process flow for manufacturing asemiconductor device. The semiconductor structures described below donot form a complete semiconductor device. Only those process acts andstructures necessary to understand the embodiments of the presentdisclosure are described in detail below. Additional acts to form thecomplete semiconductor device from the intermediate semiconductorstructures may be performed by conventional fabrication techniques. Alsonote, any drawings accompanying the present application are forillustrative purposes only, and are thus not drawn to scale.Additionally, elements common between figures may retain the samenumerical designation.

As used herein, relational terms, such as “first,” “second,” “over,”“top,” “bottom,” “underlying,” etc., are used for clarity andconvenience in understanding the disclosure and accompanying drawingsand does not connote or depend on any specific preference, orientation,or order, except where the context clearly indicates otherwise.

FIGS. 1A through 1E, are simplified partial cross-sectional viewsillustrating embodiments of a method of forming at least one metalstructure for a semiconductor device structure, such as an activeelectrode of a memory cell (e.g., for a CBRAM device), a conductiveinterface in a via, or a nucleation site. Referring to FIG. 1A,semiconductor device structure 100 may include an electrode 102, anactive material 104, and a block copolymer material 106. The activematerial 104 may be formed over and in contact with the first electrode102, and the block copolymer material 106 may be formed over and incontact with the active material 104.

The electrode 102 may include any suitable conductive materialincluding, but not limited to, a metal, a metal alloy, a conductivemetal oxide, or combinations thereof. For example, the first electrode102 may be formed from tungsten (W), tungsten nitride (WN), nickel (Ni),tantalum nitride (TaN), platinum (Pt), gold (Au), titanium nitride(TiN), titanium silicon nitride (TiSiN), titanium aluminum nitride(TiAlN), molybdenum nitride (MoN), or a combination thereof. In at leastsome embodiments, the first electrode 102 is formed from W. Theelectrode 102 may be formed in, on, or over a substrate (not shown)using conventional techniques, such as chemical vapor deposition (CVD),physical vapor deposition (PVD), or atomic layer deposition (ALD). Asused herein, the term “substrate” means and includes a base material orconstruction upon which additional materials are formed. The substratemay be a semiconductor substrate, a base semiconductor layer on asupporting structure, a metal electrode or a semiconductor substratehaving one or more layers, structures or regions fondled thereon. Thesubstrate may be a conventional silicon substrate or other bulksubstrate comprising a layer of semiconductive material. As used herein,the term “bulk substrate” means and includes not only silicon wafers,but also silicon-on-insulator (SOI) substrates, such assilicon-on-sapphire (SOS) substrates and silicon-on-glass (SOG)substrates, epitaxial layers of silicon on a base semiconductorfoundation, and other semiconductor or optoelectronic materials, such assilicon-germanium, germanium, gallium arsenide, gallium nitride, andindium phosphide. The substrate may be doped or undoped.

The active material 104 may be a solid state electrolyte material, suchas at least one of a chalcogenide compound, a transition metal oxide,and a silicon oxide. As used herein, the term “chalcogenide compound”refers to a binary or multinary compound that includes at least onechalcogen and a more electropositive element or radical. As used herein,the term “chalcogen” refers to an element of Group VI of the PeriodicTable, such as oxygen (O), sulfur (S), selenium (Se), or tellurium (Te).The electropositive element may include, but is not limited to, nitrogen(N), silicon (Si), nickel (Ni), gallium (Ga), germanium (Ge), arsenic(As), silver (Ag), indium (In), tin (Sn), antimony (Sb), gold (Au), lead(Pb), bismuth (Bi), or combinations thereof. The chalcogenide compoundmay be a binary, ternary, or quaternary alloy. As used herein, the term“transition metal oxide” means and includes an oxide of an element ofGroups VB, VIB, VIIB, VIII, IB, and IIB of the Periodic Table, such ascopper oxide (CuO), cobalt oxide (CoO), iron oxide (Fe₂O₃), nickel oxide(NiO), magnesium oxide (MnO₂), zinc oxide (ZnO), and titanium oxide(TiO₂). The silicon oxide may, for example, be silicon dioxide (SiO₂).In at least some embodiments, the active material 104 is SiO₂. Theactive material 104 may be formed over and in contact with the electrode102 using conventional techniques, such as CVD, PVD, or ALD.

As used herein, the term “block copolymer material” means and includes apolymer material including two or more polymer blocks covalently boundto one or more polymer blocks of unlike type. The block copolymermaterial 106 may be selected based on an ability of at least one polymerblock to form a complex with a metal precursor, as described in furtherdetail below. At least one of the polymer blocks may include at leastone functional group that is configured to interact with the metalprecursor to form the complex. The block copolymer material 106 may be adiblock copolymer material (i.e., copolymer material including twopolymer blocks), a triblock copolymer (i.e., a copolymer materialincluding three polymer blocks), or a multiblock copolymer (i.e., acopolymer material including more than three polymer blocks). Thedifferent polymer blocks of the block copolymer material may besubstantially immiscible in one another. By way of non-limiting example,the block copolymer material 106 may be a diblock copolymer including ahydrophobic block and a hydrophilic block. The hydrophobic block mayinclude a polymer substantially insoluble in a solvent (e.g., an inertpolar solvent, such as at least one of water and an organic solvent,such as an alcohol, tetrahydrofuran, and diemthylformamide). Thehydrophilic block may include a polymer that swells upon contact withthe solvent. In at least some embodiments, the block copolymer materialis polystryene-block-poly-2-vinylpryidine (PS-2-P2VP). A ratio of thehydrophilic block to the hydrophobic block may be within a range of fromabout 80:20 by weight to about 50:50 by weight and, such as about 70:30by weight. The block copolymer material 106 may be applied over and incontact with the active material 104 by conventional techniques, such asspin casting, spin coating, spraying, ink coating, or dip coating.

Referring to FIG. 1B, an annealing process may be used to initiate phaseseparation between polymer blocks of the block copolymer material 106(FIG. 1A) to form a block copolymer assembly 108 including at least twodifferent domains. The block copolymer assembly 108 may be formed fromthe block copolymer material 106 (FIG. 1A) by conventional self-assemblytechniques, which are not described in detail herein. The at least twodifferent domains may include at least one first domain 110 (e.g., atleast one minority domain) and at least one second domain 112 (e.g., atleast one majority domain). One or more of the at least one first domain110 and the at least one second domain 112 may include features (e.g.,cylinders, or lamellae) that extend linearly along a direction normal toa planar surface (e.g., top surface) of at least one of the electrode102 and the active material 104. When the block copolymer material 106(FIG. 1A) is a diblock copolymer including a hydrophobic block and ahydrophilic block, the at least one first domain 110 may correspond tothe hydrophilic block and the at least one second domain 112 maycorrespond to the hydrophobic block. The annealing process may, forexample, include at least one of thermal annealing (e.g., at atemperature greater than the glass transition temperature of the blockcopolymer material 106 and less than the degradation temperature of theblock copolymer material 106), solvent vapor-assisted annealing (e.g.,at a temperature greater than or equal to room temperature), andsupercritical fluid-assisted annealing. By way of non-limiting example,the block copolymer material 106 may be thermally annealed by exposingthe block copolymer material 106 to a temperature within a range of fromabout 130° C. to about 275° C. in a vacuum or an inert atmosphere (e.g.,a nitrogen atmosphere, an argon atmosphere, or combinations thereof).

Referring to FIG. 1C, the block copolymer assembly 108 (FIG. 1B) may beexposed to a staining agent 114 to form a metal-complexed blockcopolymer assembly 116 including at least one metal-complexed domain 118and at least one non-metal-complexed domain 120. As depicted in FIG. 1C,the at least one first domain 110 (FIG. 1B) may become the at least onemetal-complexed domain 118 and the at least one second domain 112 (FIG.1B) may become the at least one non-metal-complexed domain 120. Inadditional embodiments, the at least one first domain 110 (FIG. 1B) maybecome the at least one non-metal-complexed domain 120 and the at leastone second domain 112 (FIG. 1B) may become the at least onemetal-complexed domain 118.

The staining agent 114 may include at least one metal precursor 122. Theat least one metal precursor 122 may be an elemental metal, an elementalmetalloid, or a metal-containing compound capable of selectivelycoupling with the polymer of one or more domain(s) (e.g., the at leastone first domain 110 (FIG. 1B)) of the at least two different domainsrelative to the polymer of one or more other domain(s) (e.g., the atleast one second domain 112 (FIG. 1B)) of the at least two differentdomains. Suitable elemental metals may, for example, include copper,silver, ruthenium, cobalt, nickel, titanium, tungsten, tantalum,molybdenum, platinum, palladium, iridium, gold, and iron. Suitableelemental metalloids may, for example, include silicon, and germanium.Suitable metal-containing compounds may, for example, include metaloxides (e.g., metal alkoxide), and metal salts (e.g., metal halides,metal sulfates, metal cyanides, metal nitrides, and metal nitrates).Optionally, the staining agent 114 may also include at least onesolvent. The at least one solvent may be a liquid, gas, or vapor capableof selectively permeating and swelling the one or more domain(s) (e.g.,the at least one minority domain 110 (FIG. 1B)) of the at least twodifferent domains relative to the one or more other domain(s) (e.g., theat least one majority domain 112 (FIG. 1B)) of the at least twodifferent domains. In at least some embodiments, the staining agent 114is a mixture of the metal precursor 122 and at least one solvent.

Exposing the block copolymer assembly 108 (FIG. 1B) to the stainingagent 114 may form the metal-complexed block copolymer assembly 116through at least one of chelation, other ligand interactions, andcoulombic interactions. As a non-limiting example, at least where themetal precursor 122 is an elemental metal or an elemental metalloid andthe polymer of one or more domain(s) (e.g., the at least one firstdomain 110 (FIG. 1B)) includes at least one of unsaturated organicgroups (i.e., organic groups having π-orbital electrons) and one or moreelement(s) of Groups VA and VIA of the Periodic table of Elements (e.g.,nitrogen, phosphorus, sulfur, and oxygen) in appropriate spacings andorientations, the polymer of the one or more domain(s) may coordinatewith the elemental metal or the elemental metalloid (e.g.,charge-neutral forms, and charge-positive forms) through chelationand/or other ligand interactions. As an additional non-limiting example,at least where the metal precursor 122 is a metal-containing compound,the metal precursor 122 may be selectively coupled to the polymer of oneor more domain(s) (e.g., the at least one minority domain 110 (FIG. 1B))through coulombic interactions by providing a charge to the polymer ofthe one or more domain(s) opposing a charge provided to themetal-containing compound. For instance, if the polymer of one or moredomain(s) (e.g., the at least one minority domain 110 (FIG. 1B))includes cationic functionality (e.g., functional groups or constituentsthat are or may become positively charged, such as pyridine), thestaining agent 114 may be an aqueous acid solution including ametal-containing compound including anionic functionality (e.g.,functional groups or constituents of the metal-containing compound thatare or may become negatively charged). Conversely, if the polymer of oneor more domain(s) (e.g., the at least one minority domain 110 (FIG. 1B))includes anionic functionality (e.g., functional groups or constituentsthat are or may become negatively charged, such as carboxylic acidgroups or thiol groups), the staining agent 114 may be an aqueous basesolution including a metal-containing compound including cationicfunctionality (e.g., functional groups or constituents of themetal-containing compound that are or may become positively charged).

Table 1 below is a non-limiting list of materials and conditions thatmay be used in combination to form the at least one metal-complexeddomain 118 of the metal-complexed block copolymer assembly 116.

TABLE 1 Exemplary Materials and Conditions for Forming theMetal-Complexed Domain 118 Domain Complexation Binding Metal polymer pHFunctionality precursor Poly(vinylpyridine) less than 7 PyridiniumAmmonium (i.e., acidic) silver (I) thiosulfate Poly(vinylpyridine) lessthan 7 Pyridinium Copper (II) (i.e., acidic) chloride Poly((meth)acrylicacid) greater than 7 Carboxylic acid Silver (I) (i.e., basic) nitratePoly((meth)acrylic acid) greater than 7 Carboxylic acid Copper (I)(i.e., basic) chloride

In additional embodiments, the block copolymer assembly 108 (FIG. 1B)may be exposed to the solvent and the metal precursor 122 describedabove in a multiple act process. By way of non-limiting example, theblock copolymer assembly 108 (FIG. 1B) may be exposed to the solventprior to being exposed to the metal precursor 122. Such a multiple actprocess may be used to provide the at least one minority domain 110(FIG. 1B) with an exposed surface (e.g., where the at least one minoritydomain 110 is covered by the majority domain 112), or to at leastprovide the at least one minority domain 110 (FIG. 1B) with additionalsurface area for interaction with the metal precursor 122.

Accordingly, a semiconductor device structure of the present disclosuremay include an electrode, and at least one metal-complexed structure(e.g., at least one metal-complexed domain) overlying the electrode andincluding at least one of an elemental metal, an elemental metalloid, ametal oxide, and a metal salt coupled to a polymer including featuresthat extend linearly along a direction normal to a planar surface of theelectrode.

Referring next to FIG. 1D, the polymer of the at least onenon-metal-complexed domain 120 may be volatized and removed from themetal-complexed block copolymer assembly 116 (FIG. 1C), and the metalprecursor 122 (FIG. 1C) within the at least one metal-complexed domain118 (FIG. 1C) may be reduced (i.e., chemically reduced) to form at leastone metal structure 124 over and in contact with the active layer 104.The at least one metal structure 124 may be formed of a plurality ofmetal particles (not shown). Each metal particle of the plurality ofmetal particles may be discontinuous or discrete from each other metalparticle of the plurality of metal particles. The polymer may, forexample, be volatized and removed by performing a thermal anneal in areducing atmosphere. The thermal anneal may expose the metal-complexedblock copolymer assembly 116 (FIG. 1C) to a temperature greater than orequal to a decomposition temperature of the polymer of each of the atleast one metal-complexed domain 118 (FIG. 1C) and the at least onenon-metal-complexed domain 120 (FIG. 1C). By way of non-limitingexample, the metal-complexed block copolymer assembly 116 may be exposedto a temperature with a range of from about 250° C. to about 750° C. inat least one of an ammonia atmosphere and a hydrogen atmosphere. Asshown in FIG. 1D, during the thermal anneal, at least a portion of themetal structure 124 may diffuse into the active layer 104. Conventionalprocesses (e.g., electroless plating) may, optionally, be used toincrease the size of the metal particles (not shown) of the at least onemetal structure 124.

The metal-complexed block copolymer assembly 116 (FIG. 1C) may,optionally, be exposed to an oxidizing agent (e.g., air, oxygen,nitrogen dioxide, water, nitrous oxide, dinitrogen tetroxide, ozone, orcombinations thereof) prior to performing the thermal anneal in thereducing atmosphere described above. Exposure to the oxidizing agent mayconvert the metal precursor 122 (FIG. 1C) within the at least onemetal-complexed domain 118 (FIG. 1C) to a metal oxide (not shown), whichmay then be reduced to metal by the thermal anneal in the reducingatmosphere. By way of non-limiting example, the semiconductor devicestructure 100 may be exposed to the oxidizing agent (e.g., ozone) in asealed chamber at a temperature within a range of from about 25° C. toabout 200° C., such as from about 75° C. to about 100° C., for a periodof time within a range of from about 30 seconds to about 30 hours, suchas from about 30 seconds to about 15 hours, or from about 30 seconds toabout 1 hour, or from about 10 minutes to about 1 hour. Exposing themetal-complexed block copolymer assembly 116 (FIG. 1C) to the oxidizingagent prior to performing the thermal anneal in the reducing atmospheremay enable the thermal anneal to be performed at a lower temperature,decreasing aggregation of the metal particles (not shown). In additionalembodiments, after exposing the metal-complexed block copolymer assembly116 (FIG. 1C) to the oxidizing agent, the thermal anneal in the reducingatmosphere may be omitted, leaving a metal-oxide-complexed blockcopolymer assembly (not shown) including at least onemetal-oxide-complexed domain (not shown) and at least onenon-metal-oxide-complexed domain (not shown). Polymer of themetal-oxide-complexed block copolymer assembly may be volatilized andremoved (e.g., by way of a thermal anneal) to form at least one metaloxide structure.

Accordingly, a method of forming a memory cell may include forming ablock copolymer assembly including at least two different domains overan electrode. The at least one metal precursor may be selectivelycoupled to the block copolymer assembly to form a metal-complexed blockcopolymer assembly including at least one metal-complexed domain and atleast one non-metal-complexed domain. The metal-complexed blockcopolymer assembly may be annealed to form at least one metal structure.

Referring to FIG. 1E, a structure 126, such as an electrode or acontact, may be formed over and in contact with the at least one metalstructure 124. The structure 126 may, for example, include a suitableconductive material including, but not limited to, a metal, a metalalloy, a conductive metal oxide, or combinations thereof. By way ofnon-limiting example, the structure 126 may be formed of W, WN, Ni, TaN,Pt, Ru, Co, CoSi, TiN, TiSiN, TiAlN, or MoN. The structure 126 may beformed of substantially the same material as the electrode 102 or may bea different material than the electrode 102. In at least someembodiments, the structure 126 is formed from W. The structure 126 maybe formed over and in contact with the at least one metal structure 124using conventional deposition (e.g., CVD, ALD, or PVD) and patterning(e.g., masking and etching) techniques.

FIGS. 2A through 2F, are simplified partial cross-sectional views of asemiconductor device structure 200 illustrating embodiments of anothermethod of forming at least one metal structure for a semiconductordevice structure, such as an active electrode of a memory cell (e.g.,for a CBRAM device), a conductive interface in a via, or a nucleationsite. The semiconductor substrate 200 is substantially similar to thesemiconductor substrate 100 described above, except that the metalstructures are directly formed on an electrode. Referring to FIG. 2A,the semiconductor structure 200 may include an electrode 202, and ablock copolymer material 206. The block copolymer material 206 may beformed over and in contact with the electrode 202, which may be formedin, on, or over a substrate (not shown). The electrode 202 and the blockcopolymer material 206 may be substantially similar to the electrode 102and the block copolymer material 106 described above, respectively. Theelectrode 202 and the block copolymer material 206 may be formed in aprocess substantially similar to that described above to form theelectrode 102 and the block copolymer material 106, respectively.

Referring next to FIG. 2B, an annealing process may be used to initiatephase separation between blocks of the block copolymer material 206 toform a block copolymer assembly 208 including at least one minoritydomain 210 and at least one majority domain 212. The annealing processmay be substantially similar to that described above with respect toformation of the block copolymer assembly 108. The block copolymerassembly 208, the at least one first domain 210, and at least one seconddomain 212 may be substantially similar to the block copolymer assembly108, the at least one first domain 110, and at least one second domain112 described above, respectively. As shown in FIG. 2C, the blockcopolymer assembly 208 (FIG. 2B) may be exposed to a staining agent 214at least including a metal precursor 222 to form a metal-complexed blockcopolymer assembly 216 including at least one metal-complexed domain 218and at least one non-metal-complexed domain 220. The process may besubstantially similar to that described above in relation to forming themetal-complexed block copolymer assembly 116. The staining agent 214,the metal-complexed block copolymer assembly 216, the at least onemetal-complexed domain 218, and the at least one non-metal-complexeddomain 220 may be substantially similar to the staining agent 114, themetal-complexed block copolymer assembly 116, the at least onemetal-complexed domain 118, and the at least one non-metal-complexeddomain 120 described above, respectively.

Referring next to FIG. 2D, polymer material may be volatized and removedfrom the metal-complexed block copolymer assembly 216, and the metalprecursor 222 (FIG. 2C) in the at least one metal-complexed domain 218(FIG. 2C) may be reduced to form at least one metal structure 224 overand in contact with the electrode 202. The at least one metal structure224 may be formed of a plurality of metal particles (not shown). Eachmetal particle of the plurality of metal particles may be discontinuousor discrete from each other metal particle of the plurality of metalparticles. The process may be substantially similar to that describedabove in relation to forming the at least one metal structure 124. Theat least one metal structure 224 may be substantially similar to the atleast one metal structure 124 described above. Conventional processes(e.g., electroless plating) may, optionally, be used to increase thesize of the metal particles (not shown) of the at least one metalstructure 224.

The metal-complexed block copolymer assembly 216 (FIG. 2C) may,optionally, be exposed to an oxidizing agent before forming the at leastone metal structure 224. Exposure to the oxidizing agent may convert themetal precursor 222 (FIG. 1C) within the at least one metal-complexeddomain 218 (FIG. 2C) to a metal oxide (not shown), which may then bereduced to metal by thermal anneal in a reducing atmosphere. The processmay be substantially similar to that described above in relation to thetreatment of the metal-complexed block copolymer assembly 116. Inadditional embodiments, after exposing the metal-complexed blockcopolymer assembly 216 (FIG. 1C) to the oxidizing agent, the thermalanneal in the reducing atmosphere may be omitted, leaving ametal-oxide-complexed block copolymer assembly (not shown) including atleast one metal-oxide-complexed domain (not shown) and at least onenon-metal-oxide-complexed domain (not shown). Polymer of themetal-oxide-complexed block copolymer assembly (not shown) may bevolatilized and removed (e.g., by way of a thermal anneal) to form atleast one metal oxide structure.

As shown in FIG. 2E, an active material 204 may be formed over and incontact with the at least one metal structure 224 and the electrode 202.The active material 204 may be substantially similar to the activematerial 104 described above, and may be formed using conventionaltechniques, such as CVD, PVD, or ALD, which are not described in detailherein. Referring to FIG. 2F, a structure 226, such as an electrode orcontact, may be formed over and in contact with the active material 204at a position overlying the at least one metal structure 224. Thestructure 226 may be formed using conventional deposition and patterningtechniques, which are not described in detail herein. The structure 226may be substantially similar to the structure 126 described above.

FIGS. 3A through 3E, are simplified partial cross-sectional views of asemiconductor device structure 300 illustrating embodiments of yetanother method of forming at least one metal structure for asemiconductor device structure, such as an active electrode of a memorycell (e.g., for a CBRAM device), a conductive interface in a via, or anucleation site. Referring to FIG. 3A, the semiconductor devicestructure 300 may include an electrode 302, an active material 304, anda polymer material 306. The active material 304 may be formed over andin contact with the electrode 302, and the polymer material 306 may beformed over and in contact with the active material 304. The electrode302 may be formed in, on, or over a substrate (not shown). In additionalembodiments, the active material 304 may, at least initially, beomitted, and the polymer material 306 may be formed over and in contactwith the electrode 302.

The electrode 302 and the active material 304 may be substantiallysimilar to the electrode 102 and the active material 104 describedabove, respectively. Each of the electrode 302 and the active material304 may be formed using conventional techniques, such as PVD, CVD, orALD. The polymer material 306 may be a homopolymer or a copolymer. Asused herein, the term “homopolymer” means and includes a materialresulting from the polymerization of a single monomeric species. Thepolymer material 306 may be capable of forming a complex with a metalprecursor. The polymer material 306 may, by way of non-limiting example,be a hydrophilic polymer. In at least some embodiments, the polymermaterial 306 is poly-2-vinylpyridine (P2VP). The polymer material 306may be formed over and in contact with the active material 304 byconventional techniques, such as grafting. As a non-limiting example,the polymer material 306 may be prepared with end groups (e.g., hydroxylgroups) that may interact (e.g., by forming covalent bonds) with theactive material 304.

Referring to FIG. 3B, a portion of the polymer material 306 (FIG. 3A)may be selectively removed to form a polymer pattern 308 including atleast one polymer structure 310 and at least one opening 312. Removingthe portion of the polymer material 306 (FIG. 3A) may expose a surfaceof the active material 304 or, if the active material 304 is absent, asurface of the electrode 302. The polymer pattern 308 may be formedusing conventional techniques. By way of non-limiting example, a resistmaterial (not shown), such as a conventional photoresist or aconventional e-beam resist, may be applied over the polymer material 306(FIG. 3A) and patterned using appropriate lithography techniques to forma patterned resist (not shown). The pattern defined by the patternedresist (not shown) may be transferred into the polymer material 306(FIG. 3A) using at least one dry etching process, such as reactive ionetching (RIE), plasma etching, reactive ion beam etching, or chemicallyassisted ion beam etching. Following the dry etching process, thepatterned resist (not shown) may be removed using conventionaltechniques, such as a solvent strip utilizing a solvent with which thepolymer is substantially immiscible. In additional embodiments, thepolymer material 306 may be a stainable photoresist including a blend ofphotoactive species and chemically active species. The photoactivespecies may enable photoimaging, and the chemically active species mayenable staining.

Referring next to FIG. 3C, the polymer pattern 308 (FIG. 3B) may beexposed to a staining agent 314 to form a metal-complexed polymerpattern 316 including at least one metal-complexed polymer structure 318and the at least one opening 312. The staining agent 314 and process offorming the metal-complexed polymer pattern 316 may be substantiallysimilar to the staining agent 114 and process of forming of themetal-complexed copolymer assembly 116 described above. However, whereasthe staining agent 114 may enable the selective coupling of the metalprecursor 122 included therein with the polymer of the at least oneminority domain 110, the staining agent 314 may enable the selectivecoupling of metal precursor 322 included therein with the polymer of theat least one polymer structure 310 (FIG. 3B).

Referring to FIG. 3D, the polymer material may be volatized and removedfrom the at least one metal-complexed polymer structure 318 (FIG. 3C),and the metal precursor 322 (FIG. 3C) present therein may be reduced toform at least one metal structure 324 over and in contact with theactive layer 304. The process may be substantially similar to thatdescribed above with respect to the formation of the at least one metalstructure 124. The at least one metal structure 324 may be substantiallysimilar to the at least one metal structure 124 described above and maybe formed of a plurality of metal particles (not shown). Each metalparticle of the plurality of metal particles may be discontinuous ordiscrete from each other metal particle of the plurality of metalparticles. Conventional processes (e.g., electroless plating) may,optionally, used to increase the size of the metal particles (not shown)of the at least one metal structure 324.

The at least one metal-complexed polymer structure 318 (FIG. 3C) may,optionally, be exposed to an oxidizing agent before forming the at leastone metal structure 324. Exposure to the oxidizing agent may convert themetal precursor 322 (FIG. 3C) within the at least one metal-complexedpolymer structure 318 (FIG. 3C) to a metal oxide (not shown), which maythen be reduced to metal by thermal anneal in a reducing atmosphere. Theprocess may be substantially similar to that described above in relationto the treatment of the metal-complexed block copolymer assembly 116. Inadditional embodiments, after exposing the at least one metal-complexedpolymer structure 318 (FIG. 3C) to the oxidizing agent, the thermalanneal in the reducing atmosphere may be omitted, leaving at least onemetal-oxide-complexed polymer structure (not shown). Polymer of themetal-oxide-complexed polymer structure (not shown) may be volatilizedand removed (e.g., by way of a thermal anneal) to form at least onemetal oxide structure.

In additional embodiments, such as where the active material 304 isinitially omitted, the at least one metal structure 324 may be formedover and in contact with the electrode 302, in a process substantiallysimilar to that described above in relation to forming the at least onemetal structure 224. The active material 304 may then be formed over andin contact with the at least one metal structure 324 and the electrode302, in a process substantially similar to that described above inrelation to forming the active material 204.

Accordingly, a method of forming a memory cell may include forming apolymer material over an electrode. A portion of the polymer materialmay be removed to form a polymer pattern including at least one polymerstructure and at least one opening. The polymer pattern may be exposedto a staining agent to form a metal-complexed polymer pattern includingat least one metal-complexed polymer structure. The metal-complexedpolymer pattern may be treated to form at least one metal structure.

Referring to FIG. 3E, a structure 326, such as an electrode or contact,may be formed over and in contact with the at least one metal structure324. The structure 326 may be formed using conventional deposition(e.g., CVD, ALD, or PVD) and patterning (e.g., masking and etching)techniques. The structure 326 may be substantially similar to thestructure 126 described above. In additional embodiments, such as wherethe active material 304 is formed over and in contact with the at leastone metal structure 324 and the electrode 302, the structure 326 may beformed over and in contact with the active material 304 at a positionoverlying the at least one metal structure 324, in a processsubstantially similar to that described above in relation to forming thestructure 226.

FIGS. 4A through 4G, are simplified partial cross-sectional views of asemiconductor device structure 400 illustrating embodiments of yet stillanother method of forming at least one metal structure for asemiconductor device structure, such as an active electrode of a memorycell (e.g., for a CBRAM device), a conductive interface in a via, or anucleation site. Referring to FIG. 4A, the semiconductor devicestructure 400 may include an electrode 402 and a patterned dielectricmaterial 404. The patterned dielectric material 404 may be formed overand in contact with the electrode 402. The electrode 402 may besubstantially similar to the electrode 102 described above, and may beformed in, on, or over a substrate (not shown) using conventionaltechniques, such as PVD, CVD, or ALD. The patterned dielectric material404 may include at least one dielectric structure 406 and at least oneopening 408. The at least one opening 408 may be defined by a surface405 of the electrode 404 and at least one sidewall 407 of the at leastone dielectric structure 406. The at least one dielectric structure 406may, by way of non-limiting example, include at least one of siliconoxynitride (SiON), silicon nitride (Si₃N₄), silicon dioxide (SiO₂),another oxide material, and another polymer material. In at least someembodiments, the dielectric structure 406 is formed from Si₃N₄. Thepatterned dielectric material 404 may be formed using conventionaldeposition and patterning techniques, such as PVD, CVD, or ALDdeposition followed by masking and etching. A conformal film of activematerial (not shown) may, optionally, be formed over and in contact withthe patterned dielectric material 404 (e.g., the conformal film ofactive material may cover surfaces of the at least one dielectricstructure 406 and the surface 405 of the electrode 404). If present, theconformal film of active material (not shown) may be substantiallysimilar to the active material 104 described above, and may be formedusing conventional techniques, such as PVD, CVD, or ALD.

Referring next to FIG. 4B, a polymer material 410 may be formed over andin contact with a surface 412 of the at least one dielectric structure406, the at least one sidewall 407 of the at least one dielectricstructure 406, and the surface 405 of the electrode 404 exposed by theat least one opening 408. The polymer material 410 may cover orencompass the at least one dielectric structure 406 and may at leastpartially fill the at least one opening 408. In at least someembodiments, the polymer material 410 substantially fills the at leastone opening 408. The polymer material 410 may be substantially similarto the polymer material 306 described above. In at least someembodiments, the polymer material 410 is P2VP. The polymer material 410may be formed over and in contact with the patterned dielectric material404 by conventional grafting techniques. As a non-limiting example, thepolymer material 410 may be prepared with end groups (e.g., hydroxylgroups) that may interact (e.g., by forming covalent bonds) with one ormore of the surface 412 of the at least one dielectric structure 406,the at least one sidewall 407 of the at least one dielectric structure406, and the surface 405 of the electrode 404 exposed by the at leastone opening 408.

Referring to FIG. 4C, a portion of the polymer material 410 (FIG. 4B)may be removed to expose the surface 412 of the at least one dielectricstructure 406 and form an assembly 414 including the at least onedielectric structure 406 and at least one polymer structure 416. Theportion of the polymer material 410 (FIG. 4B) may be removed usingconventional techniques, such as at least one of an abrasiveplanarization process (e.g., chemical mechanical planarization), and asuitable etching process (e.g., wet etching, dry etching).

Referring next to FIG. 4D, the assembly 414 (FIG. 4C) may be exposed toa staining agent 418 to form a metal-complexed assembly 420 including atleast one metal-complexed polymer structure 422 and the at least onedielectric structure 406 (i.e., a non-metal-complexed structure). Thestaining agent 418 and process of forming the metal-complexed assembly420 may be substantially similar to the staining agent 114 and processof forming of the metal-complexed copolymer assembly 116 describedabove. However, whereas the staining agent 114 may enable selectivecoupling of the metal precursor 122 included therein with the polymer ofthe at least one minority domain 110, the staining agent 418 may enablethe selective coupling of a metal precursor 426 included therein withthe polymer of the at least one polymer structure 416 (FIG. 4C).

In additional embodiments, the polymer material 410 (FIG. 4B) may beexposed to the staining agent 418 to form a metal-complexed polymermaterial (not shown). A portion of the metal-complexed polymer materialmay then be removed to form the metal-complexed assembly 420 includingthe at least one metal-complexed polymer structure 422 and the at leastone dielectric structure 406.

Referring to FIG. 4E, polymer material may be volatized and removed fromthe at least one metal-complexed polymer structure 422 (FIG. 4D), andthe metal precursor 426 (FIG. 4D) present therein may be reduced to format least one metal structure 428 over and in contact with the electrode402. The at least one metal structure 428 may be formed from a pluralityof metal particles (not shown). Each metal particle of the plurality ofmetal particles may be discontinuous or discrete from each other metalparticle of the plurality of metal particles. The process may besubstantially similar to that described above in relation to forming theat least one metal structure 124. However, as depicted in FIG. 4E, theat least one dielectric structure 406 may remain following the process.The at least one metal structure 428 may be substantially similar to theat least one metal structure 124 described above. Conventional processes(e.g., electroless plating) may, optionally, be used to increase thesize of the metal particles (not shown) of the at least one metalstructure 428.

The at least one metal-complexed polymer structure 422 (FIG. 4D) may,optionally, be exposed to an oxidizing agent before forming the at leastone metal structure 428. Exposure to the oxidizing agent may convert themetal precursor 426 (FIG. 4D) within the at least one metal-complexedpolymer structure 422 (FIG. 4D) to a metal oxide (not shown), which maythen be reduced to metal by thermal anneal in a reducing atmosphere. Theprocess may be substantially similar to that described above in relationto the treatment of the metal-complexed block copolymer assembly 116. Inadditional embodiments, after exposing the at least one metal-complexedpolymer structure 422 (FIG. 4D) to the oxidizing agent, the thermalanneal in the reducing atmosphere may be omitted, leaving at least onemetal-oxide-complexed polymer structure (not shown). Polymer of themetal-oxide-complexed polymer structure (not shown) may be volatilizedand removed (e.g., by way of a thermal anneal) to form at least onemetal oxide structure.

Referring next to FIG. 4F, an active material 430 may be formed over andin contact with the at least one metal structure 428 and the at leastone dielectric structure 406. The active material 430 may be formedusing conventional techniques, such as CVD, PVD, or ALD. The activematerial 430 may be substantially similar to the active material 104described above. In additional embodiments, the active material 430 maybe selectively formed over and in contact with the at least one metalstructure 428 (e.g., the active material 430 may be selectively grown onthe at least one metal structure 428). As shown in FIG. 4G, a structure432, such as an electrode or contact, may be formed over and in contactwith at least a portion of the active material 430 at a positionoverlying the at least one metal structure 428. The structure 432 may besubstantially similar to the second electrode 126 described above, andmay be formed using conventional deposition (e.g., CVD, ALD, or PVD) andpatterning (e.g., masking and etching) techniques. At least a portion ofthe structure 432 may also contact the at least one dielectric structure406.

FIGS. 5A through 5F are simplified partial cross-sectional views of asemiconductor device structure 500 illustrating embodiments of yet stillan additional method of forming at least one metal structure for asemiconductor structure, such as an active electrode of a memory cell(e.g., for a CBRAM device), a conductive interface in a via, or anucleation site. Referring to FIG. 5A, the semiconductor structure 500include an electrode 502, and a patterned dielectric material 504. Theelectrode 502 may be a conductive material (e.g., W, WN, Ni, TaN, Pt,Au, TiN, TiSiN, TiAlN, or MoN) that is reactive with a polymer materialto be grafted on a surface 510 thereof, as described in further detailbelow. The patterned dielectric material 504 may include at least onedielectric structure 506 and at least one opening 508. The at least oneopening 508 may be defined by the surface 510 of the electrode 502 andat least one sidewall 511 of the dielectric structure 506. The at leastone dielectric structure 506 may be a dielectric material (e.g.,amorphous carbon) that is non-reactive with the polymer material to begrafted on the surface 510 of electrode 502, as described in furtherdetail below.

Referring next to FIG. 5B, a polymer material 512 may be selectivelygrafted over and in contact with the surface 510 of the electrode 502exposed by the at least one opening 508 to form an assembly 505including the polymer material 512 and the dielectric structure 506. Thepolymer material 512 may be substantially similar to the polymermaterial 306 described above. In at least some embodiments, the polymermaterial 512 is P2VP. The polymer material 512 may be selectivelygrafted over and in contact with the portion of the surface 510 byconventional grafting techniques. As a non-limiting example, the polymermaterial 512 may be prepared with end groups (e.g., hydroxyl groups)that may interact (e.g., by forming covalent bonds) with the surface 510of the electrode 502. The dielectric structure 506 may be substantiallynon-reactive with the polymer material 512 such that the polymermaterial 512 does not become grafted to the at least one sidewall 511 ofthe dielectric structure 506. A suitable rinse may, optionally, beperformed to remove portions of the polymer material 512 not grafted tothe surface 510 of the electrode 502.

Referring to FIG. 5C, the assembly 505 (FIG. 5B) may be exposed to astaining agent 514 to form a metal-complexed assembly 516 including atleast one metal-complexed polymer structure 518 and the at least onedielectric structure 506 (i.e., a non-metal-complexed structure). Thestaining agent 514 and process of forming the metal-complexed assembly516 may be substantially similar to the staining agent 114 and processof forming of the metal-complexed copolymer assembly 116 describedabove. However, whereas the staining agent 114 may enable selectivecoupling of the metal precursor 122 included therein with the polymer ofthe at least one minority domain 110, the staining agent 514 may enablethe selective coupling of a metal precursor 520 included therein withthe polymer of the at least one polymer material 512 (FIG. 5B).

Referring to FIG. 5D, polymer material may be volatized and removed fromthe at least one metal-complexed polymer structure 518 (FIG. 5C), andthe metal precursor 520 (FIG. 5C) present therein may be reduced to format least one metal structure 522 over and in contact with the electrode502. The at least one metal structure 522 may include a plurality ofmetal particles (not shown). Each metal particle of the plurality ofmetal particles may be discontinuous or discrete from each other metalparticle of the plurality of metal particles. Conventional processes(e.g., electroless plating) may, optionally, be used to increase thesize of the metal particles (not shown) of the at least one metalstructure 522. The process of forming the metal structure 522 may besubstantially similar to that described above with respect to theformation the at least one metal structure 124. However, as depicted inFIG. 5D, the at least one dielectric structure 506 may remain followingthe process.

The at least one metal-complexed polymer structure 518 (FIG. 5C) may,optionally, be exposed to an oxidizing agent before forming the at leastone metal structure 522. Exposure to the oxidizing agent may convert themetal precursor 520 (FIG. 5C) within the at least metal-complexedpolymer structure 518 (FIG. 5C) to a metal oxide (not shown), which maythen be reduced to metal by thermal anneal in a reducing atmosphere. Theprocess may be substantially similar to that described above in relationto the treatment of the metal-complexed block copolymer assembly 116. Inadditional embodiments, after exposing the at least one metal-complexedpolymer structure 518 (FIG. 5C) to the oxidizing agent, the thermalanneal in the reducing atmosphere may be omitted, leaving at least onemetal-oxide-complexed polymer structure (not shown). Polymer of the atleast one metal-oxide-complexed polymer structure (not shown) may bevolatilized and removed (e.g., by way of a thermal anneal) to form atleast one metal oxide structure.

Accordingly, a method of forming a memory cell may include forming apatterned dielectric material including at least one dielectricstructure and at least one opening over an electrode. A polymer materialmay be formed over and in contact with at least a surface of theelectrode exposed by the at least one opening. The at least onedielectric structure and the polymer material may be exposed to astaining agent to form a metal-complexed assembly including at least onemetal-complexed polymer structure. The metal-complexed assembly may betreated to form at least one metal structure.

Referring next to FIG. 5E, an active material 524 may be formed over andin contact with the at least one metal structure 522 and the at leastone dielectric structure 506. The active material 524 may be formedusing conventional techniques, such as CVD, PVD, or ALD. The activematerial 524 may be substantially similar to the active material 104described above. In additional embodiments, the at least one dielectricstructure 506 may be removed and the active material 524 may be formedover and in contact with the at least one metal structure and theelectrode 502. As shown in FIG. 5F, a structure 526, such as anelectrode or contact, may be formed over and in contact with at least aportion of the active material 524 at a position overlying the at leastone metal structure 522. The structure 526 may be substantially similarto the structure 126 described above, and may be formed usingconventional deposition (e.g., CVD, ALD, or PVD) and patterning (e.g.,masking and etching) techniques. At least a portion of the structure 526may also contact the at least one dielectric structure 506, if present.

The methods of the present disclosure advantageously reduce metalprocessing, decrease material deposition variability relative toconventional selective deposition technologies, such as electrolessplating, and enable the formation of semiconductor structures, memorycells, and semiconductor devices that exhibit increased reliability,performance, and durability. In addition, the methods of the presentdisclosure enable the deposition of material on electrochemicallyinactive materials (e.g., dielectric materials, such as oxide materials)where conventional selective deposition technologies, such aselectroless plating, may be substantially ineffective. Structures (e.g.,metal structures, or metal oxide structures) may be formed in desiredlocations on a substantially planar material (e.g., an electrode (i.e.,a conductive material) or an active material), or in openings in apatterned material (e.g., a patterned dielectric material) that overliesa substantially planar material.

The following examples serve to explain embodiments of the presentdisclosure in more detail. The examples are not to be construed as beingexhaustive or exclusive as to the scope of the disclosure.

EXAMPLES Example 1

Two solutions of 1% P2PV in 10:1 tetrahydrofuran:diemthylformamide wereprepared. One solution included 10 wt % copper(II) chloride (CuCl₂). Theother solution included 2 wt % CuCl₂. Coupon samples were prepared byspin-coating the solutions onto a substrate stack including silicon(“Si”, 95 Å), a pad oxide layer (“PADOX”, 300 Å), nitride (30 Å), andzirconium oxide (“ZrOx”). Samples including each of the aboveconcentrations of CuCl₂ were thermally annealed for 10 minutes at 750°C. under an atmosphere of either ammonia (NH₃) or 3.8% hydrogen (H₂) inargon (Ar) according to Table 2 below.

TABLE 2 Sample Data Sample wt % CuCl₂ Reducing atmosphere F 10 H₂ H 10NH₃ J 2 H₂ L 2 NH₃

After the thermal anneal the samples were inspected by scanning electronmicrograph (SEM), Auger electron spectroscopy, and XPS. SEM imagery ofsamples F, H, and J showed the formation of white particles. FIG. 6A isa scanning electron micrograph (SEM) image showing a top-down view ofwhite particles formed from the sample F. FIG. 6B is a magnified SEMimage showing a top-down view of a single white particle formed fromsample F illustrating the two areas used for Auger analysis. The chartof Auger analysis of sample F is shown in FIG. 7A. Particles formed fromsamples H and J had similar results. An Auger electron map of the whiteparticle shown in FIG. 6B is shown in FIG. 7B. The XPS analysis resultsare shown in Table 3 below. In Table 3, samples 1, 2, 3, and 4respectively correspond to samples F, H, J, and L of Table 2. The Augerand XPS analysis results showed that the white particles formed fromsample F (i.e., sample 1 in Table 3 below) were copper and had both CuOand either Cu₂O or Cu(0) metal composition. No chlorine atoms weredetected, indicating that the particles were fully reduced and thensubsequently re-oxidized by atmospheric oxygen. The particles formedfrom samples F, H, J, and L had center diameters ranging from about 50nm to about 250 nm.

TABLE 3 XPS Analysis Data Surface elemental concentrations (in atom %)Sample C N O F So Zr Cu(o)/Cu(I) Cu(II) 1 14.8 8.6 49.0 0.5 8.4 16.4 0.81.5 2 39.9 3.0 32.5 10.3 3.2 11.2 ND ND 3 16.2 7.4 49.5 0.5 8.3 18.0 NDND 4 32.2 2.7 44.3 0.6 7.0 13.2 ND ND

Example 2

Two solutions of 1% PS-P2PV in 10:1 tetrahydrofuran:diemthylformamidewere prepared. One solution included 10 wt % copper(II) chloride(CuCl₂). The other solution included 2 wt % CuCl₂. Coupon samples wereprepared by spin-coating the solutions onto a substrate stack includingSi (95 Å), PADOX (300 Å), nitride (30 Å), and ZrOx. Two samples, one foreach of the above concentrations of CuCl₂, were thermally annealed for10 minutes at 750° C. under an atmosphere of 3.8% hydrogen (H₂) in argon(Ar).

After the thermal anneal the samples was inspected by scanning electronmicrograph (SEM) and Auger electron spectroscopy. SEM imagery for eachof the sample including 10 wt % CuCl₂ loading and the sample including 2wt % CuCl₂ loading show the formation of white particles. FIGS. 8A and8B are SEM images (i.e., at 10 k and 100 k magnification, respectively)showing a top-down view of white particles formed from the sampleincluding 10 wt % CuCl₂ loading. FIGS. 9A and 9B are SEM images (i.e.,at 10 k and 100 k magnification, respectively) showing a top-down viewof white particles formed from the sample including 2 wt % CuCl₂loading. The sample including 10 wt % CuCl₂ loading exhibited a greaterareal density of white particles, and formed particle center diametersranging from about 20 nm to about 100 nm. The sample including 2 wt %CuCl₂ loading exhibited separated clusters of white particles, andformed particle center diameters of about 50 nm. FIG. 10A is a scanningelectron micrograph (SEM) image showing a top-down view of whiteparticles formed from a sample B including 2 wt % CuCl₂. FIG. 10B is amagnified SEM image showing a top-down view of a single white particleformed from sample B illustrating the two areas used for Auger analysis.The chart of Auger analysis of sample B is shown in FIG. 11A. An Augerelectron map of the white particle shown in FIG. 10B is shown in FIG.11B. The Auger analysis results showed that the white particles formedfrom sample B were copper.

While the present disclosure is susceptible to various modifications andalternative forms, specific embodiments have been shown by way ofexample in the drawings and have been described in detail herein.However, the present disclosure is not intended to be limited to theparticular forms disclosed. Rather, the present disclosure is to coverall modifications, equivalents, and alternatives falling within thescope of the present disclosure as defined by the following appendedclaims and their legal equivalents.

What is claimed is:
 1. A method of forming a semiconductor devicestructure, comprising: forming a block copolymer assembly comprising atleast two different domains over an electrode; selectively coupling atleast one metal precursor to the block copolymer assembly to form ametal-complexed block copolymer assembly comprising at least onemetal-complexed domain and at least one non-metal-complexed domain; andannealing the metal-complexed block copolymer assembly to form at leastone metal structure over the electrode.
 2. The method of claim 1,wherein forming a block copolymer assembly comprises: applying a blockcopolymer material comprising at least two different polymer blocks overthe electrode; and separating the at least two different polymer blocksto form the at least two different domains, each of the domainscomprising at least one of the different polymer blocks.
 3. The methodof claim 1, wherein forming the block copolymer assembly comprisesforming the block copolymer assembly such that at least one of the atleast two different domains extends linearly along a direction normal toa planar surface of the electrode.
 4. The method of claim 1, furthercomprising forming an active material between the electrode and theblock copolymer assembly.
 5. The method of claim 1, further comprisingforming a structure comprising at least one of a metal, a metal alloy,and a metal oxide over and in contact with the at least one metalstructure.
 6. The method of claim 1, further comprising: forming anactive material comprising a solid state electrolyte material over theat least one metal structure and the electrode; and forming a structureover the active material at a position overlying the at least one metalstructure.
 7. The method of claim 1, wherein selectively coupling the atleast one metal precursor to the block copolymer assembly comprisesexposing the block copolymer assembly to a staining agent comprising asolvent and at least one of an elemental metal, an elemental metalloid,and a metal-containing compound.
 8. The method of claim 7, whereinexposing the block copolymer assembly to the staining agent comprisesexposing the block copolymer assembly to an aqueous acid solutioncomprising a metal-containing compound having anionic functionality. 9.The method of claim 8, wherein exposing the block copolymer assembly tothe staining agent comprises exposing the block copolymer assembly to anaqueous base solution comprising a metal-containing compound havingcationic functionality.
 10. The method of claim 1, wherein selectivelycoupling at least one metal precursor to the block copolymer assemblycomprises exposing the block copolymer assembly to a staining agentcomprising at least one of a copper compound and a silver compound. 11.The method of claim 1, wherein annealing the metal-complexed blockcopolymer assembly comprises exposing the metal-complexed blockcopolymer assembly to a temperature within a range of from about 250° C.to about 750° C. in a reducing atmosphere.
 12. The method of claim 1,wherein the at least one metal structure comprises a plurality of metalparticles.
 13. The method of claim 1, further comprising exposing themetal-complexed block copolymer assembly to an oxidizing agent beforeannealing the metal-complexed block copolymer assembly.
 14. The methodof claim 1, wherein forming a block copolymer assembly comprises:applying a block copolymer material comprising a hydrophilic block and ahydrophobic block over the electrode; and phase-separating thehydrophilic block and the hydrophobic block to form a hydrophilic domainand a hydrophobic domain.
 15. The method of claim 1, wherein forming ablock copolymer assembly comprises: applyingpolystyrene-block-poly-2-vinylpyridine over the electrode; and annealingthe polystyrene-block-poly-2-vinylpyridine.
 16. The method of claim 1,wherein forming a block copolymer assembly comprises forming one of theat least two different domains to have cationic functionality, andwherein selectively coupling at least one metal precursor to the blockcopolymer assembly comprises exposing the block copolymer assembly to atleast one of silver (I) nitrate and copper (I) chloride.
 17. The methodof claim 1, wherein forming a block copolymer assembly comprises formingone of the at least two different domains to have anionic functionality,and wherein selectively coupling at least one metal precursor to theblock copolymer assembly comprises exposing the block copolymer assemblyto at least one of ammonium silver (I) thiosulfate and copper (II)chloride.
 18. The method of claim 1, wherein selectively coupling the atleast one metal precursor to the block copolymer assembly comprisesexposing the block copolymer assembly to a staining agent comprising atleast one of copper, silver, ruthenium, cobalt, nickel, titanium,tungsten, tantalum, molybdenum, platinum, palladium, iridium, gold,iron, silicon, and germanium.
 19. The method of claim 1, whereinannealing the metal-complexed block copolymer assembly comprisesexposing the metal-complexed assembly to a reducing atmosphere and atemperature greater than or equal to a decomposition temperature ofpolymer material of the metal-complexed block copolymer assembly. 20.The method of claim 1, further comprising exposing the metal-complexedblock copolymer assembly to at least one of air, oxygen, nitrogendioxide, water, nitrous oxide, dinitrogen tetroxide, and ozone beforeannealing the metal-complexed block copolymer assembly.
 21. The methodof claim 1, further comprising: forming an active material comprising atleast one of a chalcogenide compound, a transition metal oxide, and asilicon oxide on the at least one metal structure and the electrode; andforming at least one structure on the active material at a positionoverlying the at least one metal structure.
 22. A method of forming asemiconductor device structure, comprising: forming a block copolymerassembly over an electrode, the block copolymer assembly comprising: afirst domain formulated to interact with a metal precursor through atleast one of chelation, other ligand interactions, and coulombicinteractions; and a second domain formulated to not interact with themetal precursor through at least one of chelation, other ligandinteractions, and coulombic interactions; exposing the block copolymerassembly to the metal precursor to form a metal-complexed assemblycomprising a metal-complexed domain and a non-metal-complexed domain;and treating the metal-complexed assembly to form at least one of ametal structure and a metal oxide structure over the electrode.
 23. Themethod of claim 22, wherein forming a block copolymer assembly comprisesforming the first domain to comprise unsaturated organic groups and atleast one element of Groups VA and VIA of the Periodic Table ofElements.
 24. The method of claim 22, wherein forming a block copolymerassembly comprises forming the first domain to comprise a polymer havingpyridine functional groups.
 25. The method of claim 22, wherein forminga block copolymer assembly comprises forming the first domain tocomprise poly(vinylpyridine).
 26. The method of claim 22, whereinforming a block copolymer assembly comprises forming the first domain tocomprise a polymer having at least one of carboxylic acid groups andthiol groups.
 27. The method of claim 22, wherein forming a blockcopolymer assembly comprises forming the first domain to comprisepoly((meth)acrylic acid).
 28. The method of claim 22, wherein forming ablock copolymer assembly comprises forming the second domain to comprisepolystyrene.
 29. The method of claim 22, wherein treating themetal-complexed assembly comprises annealing the metal-complexedassembly to form the metal structure over the electrode.
 30. The methodof claim 22, wherein treating the metal-complexed assembly comprises:exposing the metal-complexed assembly to an oxidizing agent to form ametal-oxide-complexed block copolymer assembly; and annealing themetal-oxide-complexed block copolymer assembly to form the metal oxidestructure over the electrode.